CN114656431A - Alpha, beta-unsaturated ketone compound and preparation method and application thereof - Google Patents

Alpha, beta-unsaturated ketone compound and preparation method and application thereof Download PDF

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CN114656431A
CN114656431A CN202210389352.5A CN202210389352A CN114656431A CN 114656431 A CN114656431 A CN 114656431A CN 202210389352 A CN202210389352 A CN 202210389352A CN 114656431 A CN114656431 A CN 114656431A
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unsaturated ketone
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张维
艾文英
金海涛
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Zhejiang Tangneng Technology Co ltd
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    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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Abstract

The application discloses an alpha, beta-unsaturated ketone compound and a preparation method and application thereof, wherein the alpha, beta-unsaturated ketone compound is selected from at least one of a compound with a structural formula shown in a formula I and a compound with a structural formula shown in a formula II. The alpha, beta-unsaturated ketone compound of the invention has strong corrosion resistance effect on carbon steel as an organic corrosion inhibitor. After the carbon steel is treated, the corrosion rate of the corrosion inhibitor is reduced by about 5 times compared with the corrosion rate of the known water-soluble imidazoline quaternary ammonium salt corrosion inhibitor.

Description

Alpha, beta-unsaturated ketone compound and preparation method and application thereof
Technical Field
The application relates to an alpha, beta-unsaturated ketone compound and a preparation method and application thereof, belonging to the technical field of corrosion inhibitors.
Background
In industrial production, before spraying an anticorrosive coating on a large steel facility, the surface of the large steel facility needs to be subjected to rust removal and sand blasting. However, conventional dry blasting processes are often accompanied by dust and noise pollution. The water sand blasting process introduced into China in the 20 th century and the 80 th century has good environmental protection compared with the traditional dry sand blasting, but is limited by the fact that secondary rust return is easy to form after rust removal, so that the process is difficult to popularize and apply on a large scale. In recent years, environmental protection laws and regulations are in turn out, the use of the traditional dry sand blasting process is strictly limited, and the water sand blasting process enters the public vision again due to the environmental protection advantage. The water-sandblasting process currently faces mainly the following two problems: firstly, after the water is sprayed with sand, the surface of steel has high humidity, so that the steel is easy to return to rust; secondly, in order to prevent rust return after water and sand blasting, a corrosion inhibitor is usually added in the water and sand blasting process, and the traditional inorganic corrosion inhibitors such as nitrite, chromate, phosphate, alkynol and the like are extremely easy to cause harm to the environment and are gradually eliminated at present.
Disclosure of Invention
According to one aspect of the application, an alpha, beta-unsaturated ketone compound, a preparation method and an application thereof are provided, wherein the alpha, beta-unsaturated ketone compound has an aromatic ring, multiple bonds and heteroatoms (N, O, S and the like), can be used as a corrosion inhibitor, and utilizes conjugated pi electrons and lone pair electrons in the heteroatoms to improve the performance of the corrosion inhibitor. The corrosion inhibitors can be tightly adsorbed on the metal surface layer through electrostatic acting force or pi-d electron interaction between metal and hetero atoms, so that a corrosive medium is effectively separated from a metal substrate, and efficient corrosion prevention is realized.
According to a first aspect of the present application, there is provided an α, β -unsaturated ketone compound selected from at least one of a compound having a structural formula shown in formula I, a compound having a structural formula shown in formula II;
Figure BDA0003594970610000011
Figure BDA0003594970610000021
in formula I, formula II, Y1Any one selected from methylene and N, O, S; y is2Any one selected from methine and N;
R1is selected from C1-C24Any one of alkyl groups of (a);
R2selected from amino, hydroxyl,*-OSO3M, a polyethoxy ether group, a substituted amino group, a polyethamino group,＊-NR3 +x1 -Any one of (a);
m is selected from any one of Na, K and Li;
R3is selected from C1-C6Alkyl, substituted C1-C6Alkyl of (C)6-C12Any one of the aryl groups of (a);
X1selected from halogens.
Optionally, the substituents in the substituted amino group are selected from C6-C12Any of the aryl groups of (1).
Optionally, the number of ethoxy units in the polyethoxy ether group is 1-10;
the number of the ethylamine units in the polyethylamine group is 1-10.
Said substituted C1-C6In the alkyl group of (1)The substituents being selected from C6-C12Any of the aryl groups of (1).
According to a second aspect of the present application, there is provided a method for producing the above α, β -unsaturated ketone compound, the method comprising:
reacting a mixture containing a compound I and a compound ii in the presence of an alkaline substance to obtain the alpha, beta-unsaturated ketone compound P;
r in the alpha, beta-unsaturated ketone compound P2Is a hydroxyl group;
the compound i is selected from any one of a compound with a structural formula shown in a formula III and a compound with a structural formula shown in a formula IV;
Figure BDA0003594970610000022
the compound ii is selected from any one of compounds with a structural formula shown in a formula V;
Figure BDA0003594970610000023
alternatively, the first and second electrodes may be,
(a) mixing the alpha, beta-unsaturated ketone compound P with a halogenating reagent, and reacting II to obtain a halogenated intermediate product K;
(b) reacting said halogenated intermediate K with a compound containing R2Reacting III with nucleophilic reagent to obtain the alpha, beta-unsaturated ketone compound O;
r in the alpha, beta-unsaturated ketone compound O2Selected from amino,*-OSO3M, a polyethoxy ether group, a substituted amino group, a polyethamino group,＊-NR3 +x1 -Any one of (a);
alternatively, the first and second electrodes may be,
mixing the alpha, beta-unsaturated ketone compound P with pyridine sulfate to react IV to obtain the alpha, beta-unsaturated ketone compound Q;
said alpha, beta-unsaturationR in ketone compound Q2Is composed of*-OSO3M。
Alternatively, the α, β -unsaturated ketones can be prepared starting from aldehydes (3) and ketones (4). First, in the presence of an alcohol compound as a solvent and an aqueous alkaline solution, aldehyde (3) and ketone (4) are added thereto, and a reaction is carried out at room temperature to prepare compound (5). The hydroxy group in the compound (5) is then chlorinated with thionyl chloride to prepare a chlorinated compound (6). Finally, nucleophilic reagent such as triethylamine, tributylamine, tribenzylamine, aniline, tetraethylene glycol and the like is used for nucleophilic substitution on the chlorine compound to prepare the compound (1). Wherein, the hydroxyl in the compound (5) can be directly sulfated by pyridine sulfate to prepare the sulfate compound which accords with the general formula (1).
Figure BDA0003594970610000031
Scheme 1: preparation route of alpha, beta-unsaturated ketone organic corrosion inhibitor
Optionally, the conditions of reaction I are: the reaction temperature is 20-30 ℃; the reaction time is 18-24 h;
the conditions of the reaction II are as follows: the reaction temperature is 10-20 ℃; the reaction time is 0.5 to 4 hours;
the conditions of the reaction III are as follows: the reaction temperature is 50-100 ℃; the reaction time is 0.5 to 5 hours;
the conditions of the reaction IV are as follows: the reaction temperature is 20-30 ℃; the reaction time is 0.5 h-2 h.
Optionally, in step (a), the halogenating agent is selected from at least one of thionyl chloride, oxalyl chloride, phosphorus oxychloride, concentrated hydrochloric acid, phosphorus tribromide;
said compound containing R2The nucleophilic reagent is at least one selected from triethylamine, tributylamine, tribenzylamine, aniline, diethylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, pentaethylene glycol, octaethylene glycol, N' -bis (2-aminoethyl) -1, 3-propanediamine, diethylenetriamine, triethylenetetramine, 1, 8-diamino-3, 6-dioxaoctane。
Alternatively, the molar ratio of said compound i to said compound ii is 0.5-1: 1-10;
in the step (a), the alpha, beta-unsaturated ketone compound P, the acyl chloride reagent and the compound containing R2The mol ratio of the nucleophilic reagent is 0.5-1:1-10: 1-10;
the mol ratio of the alpha, beta-unsaturated ketone compound P to the pyridine sulfate is 0.5-1: 1-10.
Optionally, the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, potassium phosphate.
According to a final aspect of the application, there is provided a use of at least one of the above α, β -unsaturated ketone compounds, the α, β -unsaturated ketone compounds prepared according to the above method, as corrosion inhibitors.
Optionally, the corrosion inhibitor is used for corrosion protection of carbon steel.
In this application, C1～C6Refers to the number of carbon atoms involved.
In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound. The alkane compound comprises straight-chain alkane, branched-chain alkane, cycloalkane and cycloalkane with branched chain.
In the present application, "polyethoxy ether group" means
Figure BDA0003594970610000041
n＝0,1,2…9。
In the present application, "polyethylamine group" means
Figure BDA0003594970610000042
n＝0,1,2…9。
In this application, "aryl" is a group formed by the loss of one hydrogen atom on an aromatic ring on an aromatic compound molecule; such as p-tolyl, formed by toluene losing the hydrogen atom para to the methyl group on the phenyl ring.
The beneficial effects that this application can produce include:
the alpha, beta-unsaturated ketone compound of the invention has strong corrosion resistance effect on carbon steel as an organic corrosion inhibitor. Compared with the known water-soluble imidazoline quaternary ammonium salt corrosion inhibitor, the alpha, beta-unsaturated ketone compound has stronger corrosion resistance by adopting a static weight loss method. After the carbon steel is treated, the corrosion rate of the corrosion inhibitor is reduced by about 5 times compared with the corrosion rate of the known water-soluble imidazoline quaternary ammonium salt corrosion inhibitor.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were purchased commercially.
Example 1(5- (hydroxymethyl) furan-2-yl) dec-1-en-3-one
Figure BDA0003594970610000051
The synthesis steps are as follows: 5-hydroxymethylfurfural (100mg, 1 eq), 2-nonanone (5 eq), 0.5M NaOH (0.57 eq, 0.9mL), MeOH (0.9mL), was stirred at room temperature for 12 hours, with the reaction monitored on a plaque basis (with petroleum ether PE: ethyl acetate EtOAc: 5: 1) every 5 hours. After the reactant 5-hydroxymethylfurfural disappears, adding 100mL of ethyl acetate, washing with saturated salt solution, extracting for three times, collecting an organic phase, extracting a water phase twice with ethyl acetate, combining the organic phases, adding anhydrous magnesium sulfate or anhydrous sodium sulfate, drying, filtering to remove a drying agent, concentrating the organic phase, and purifying with a silica gel column by using petroleum ether: ethyl acetate 10: 1-petroleum ether: ethyl acetate 5: gradient elution 1 to obtain the purified target product.
Example 2
N, N-diethyl-N- ((5- (3-oxo-1-en-1-yl) furan-2-yl) methyl) ethylamine chloride
Figure BDA0003594970610000052
The method comprises the following steps: to the compound (100mg, 1 eq) obtained in example 1 was added dichloromethane (1mL) to give a mixture, and thionyl chloride (1.1 eq) was slowly added dropwise to the mixture, which was stirred at room temperature for 0.5 hour, and the reaction was monitored on a plaque basis (with petroleum ether: ethyl acetate 10: 1) every 0.5 hour. And after no reactant exists, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system for three times by using the saturated sodium bicarbonate aqueous solution and saturated saline solution, combining organic solvents for three times, drying, filtering, and concentrating an organic phase to obtain a crude chloride product which is directly used for the next reaction.
Step two: to the crude chloride obtained in the previous step, acetonitrile solvent (2mL) and triethylamine (1.2 eq) were added, the reaction was carried out at 80 ℃ for 3 hours, the reaction was monitored every 1.5 hours (petroleum ether: ethyl acetate 10:1 for chlorinated starting material, DCM: MeOH: 10:1 for quaternary ammonium salt product), after the reaction was completed, the reaction solution was concentrated by a rotary evaporator, after concentration, 50mL of dichloromethane was added to the concentrated solution, the mixture was washed and extracted three times with saturated brine, and the three organic phases were combined, dried, filtered, and concentrated. Then on a silica gel column, with dichloromethane: 20 parts of methanol: 1 eluting to obtain a purified target product.
Example 3(5- (3-oxo-1-en-1-yl) furan-2-yl) sulfuric acid sodium salt
Figure BDA0003594970610000061
The synthesis steps are as follows: to the compound obtained in example 1 (100mg, 1 eq) was added pyridine sulfur trioxide complex (1 eq) and pyridine (3mL) respectively, stirred at room temperature for 12 hours, and the reaction was monitored every 1 hour time on a plaque (starting material was monitored with PE: EA ═ 5: 1, and product was monitored with dichloromethane DCM: methanol MeOH ═ 10: 1). After the reaction, the reaction solution was concentrated by a rotary evaporator (water bath temperature 65 ℃ C.), after the concentration, 1mL of methylene chloride was added to the concentrated solution, the solution was frozen and crystallized in a refrigerator (note: without shaking), and after about half an hour, the solution was taken out, and a large amount of crystalline solid was observed to be precipitated, and the obtained crystals, which were the preliminarily purified target product, were washed with petroleum ether in a Buchner funnel, followed by silica gel column chromatography with methylene chloride: 20 parts of methanol: 1 eluting to obtain a purified target product.
Example 4(5- (aminomethyl) furan-2-yl) dec-1-en-3-one
Figure BDA0003594970610000062
The synthesis steps are as follows: the method comprises the following steps: the compound obtained in example 1 (100mg, 1 equivalent) was dissolved in dichloromethane (4mL), cooled to 0 ℃, and then a solution of phosphorus tribromide (1.3 equivalents) in dichloromethane (4mL) was added dropwise thereto, and the mixture was further stirred for 1 hour, with the reaction being monitored every 0.5 hour on a time-plate. After the reaction is finished, washing with water, extracting with dichloromethane, drying with anhydrous sodium sulfate, and evaporating the solvent to obtain oily substance, namely crude bromide, which is directly used for the next reaction without further purification.
Step two: the bromide obtained in the first step was dissolved in a mixed solution of ether/ethanol (2 mL: 2mL), and aqueous ammonia (0.5mL) was added dropwise thereto, followed by stirring at room temperature for 5 hours. After the reaction is finished, washing with water, extracting with dichloromethane, drying with anhydrous sodium sulfate, evaporating the solvent to obtain oily matter which is a crude product of the target product, and then performing silica gel column chromatography on the oily matter by using petroleum ether: ethyl acetate 1:1 eluting to obtain a purified target product.
Example 5
(5- ((2- ((2-aminoethyl) amino) methyl) furan-2-yl) dec-1-en-3-one
Figure BDA0003594970610000063
The method comprises the following steps: to the compound (100mg, 1 eq) obtained in example 1 was added dichloromethane (1mL) to give a mixture, and thionyl chloride (1.1 eq) was slowly added dropwise to the mixture, which was stirred at room temperature for 0.5 hour, and the reaction was monitored on a plaque basis (with petroleum ether: ethyl acetate 10: 1) every 0.5 hour. After the reaction is finished, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system with the saturated sodium bicarbonate aqueous solution and saturated saline solution for three times, combining the organic solvents for three times, drying, filtering, and concentrating the organic phase to obtain a crude chloride product which is directly used for the next reaction.
Step two: adding acetonitrile solvent (2mL) and diethylenetriamine (1.1 equivalent) into the crude chloride obtained in the previous step, reacting for 3 hours at 80 ℃, monitoring the reaction every 1.5 hours, concentrating the reaction solution by using a rotary evaporator after the reaction is finished, adding 50mL dichloromethane into the concentrated solution after the concentration, washing and extracting for three times by using saturated saline solution, combining organic phases for three times, drying, filtering and concentrating. Then on a silica gel column, with dichloromethane: 20 parts of methanol: 1 eluting to obtain a purified target product.
Example 6
(5- ((2- (2-hydroxyethoxy) ethoxy) methyl) furan-2-yl) dec-1-en-3-one
Figure BDA0003594970610000071
The method comprises the following steps: dichloromethane (1mL) was added to the compound (100mg, 1 equivalent) obtained in example 1 to give a mixture, and thionyl chloride (1.1 equivalent) was slowly added dropwise to the mixture, and the mixture was stirred at room temperature for 0.5 hour while monitoring the reaction with a time-plate every 0.5 hour (monitoring with petroleum ether: ethyl acetate 10: 1). After the reaction is finished, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system with the saturated sodium bicarbonate aqueous solution and saturated saline solution for three times, combining the organic solvents for three times, drying, filtering, and concentrating the organic phase to obtain a crude chloride product which is directly used for the next reaction.
Step two: adding acetonitrile solvent (2mL) and diethylene glycol (1.1 equivalent) into the crude chloride obtained in the previous step, reacting for 3 hours at 80 ℃, monitoring the reaction every 1.5 hours, concentrating the reaction solution by using a rotary evaporator after the reaction is finished, adding 50mL of dichloromethane into the concentrated solution after the concentration, washing and extracting for three times by using saturated saline solution, combining organic phases obtained for three times, drying, filtering and concentrating. Then on a silica gel column, with dichloromethane: 20 parts of methanol: 1 eluting to obtain a purified target product.
Example 7(5- (hydroxymethyl) pyrrol-2-yl) dec-1-en-3-one
Figure BDA0003594970610000081
The synthesis steps are as follows: 5- (hydroxymethyl) pyrrole-2-carbaldehyde (100mg, 1 eq), 2-nonanone (10 eq), 0.5M NaOH (0.57 eq, 0.9mL), MeOH (0.9mL), stirred at room temperature for 12 h, and the reaction monitored every 5 hours on a time-pad (monitoring with petroleum ether PE: ethyl acetate EtOAc ═ 5: 1). After the reaction, 100mL of ethyl acetate is added, the mixture is washed and extracted for three times by saturated saline solution, an organic phase is collected, an aqueous phase is extracted for two times by ethyl acetate, the organic phases are combined, anhydrous magnesium sulfate or anhydrous sodium sulfate is added for drying, a drying agent is removed by filtration, the organic phase is concentrated, and the mixture is subjected to silica gel column chromatography by petroleum ether: ethyl acetate 10: 1-petroleum ether: ethyl acetate 5: gradient elution 1 to obtain the purified target product.
Example 8N, N-diethyl-N- ((5- (3-oxo-1-en-1-yl) pyrrol-2-yl) methyl) ethylamine chloride
Figure BDA0003594970610000082
The method comprises the following steps: dichloromethane (1mL) was added to the compound (100mg, 1 equivalent) obtained in example 7 to give a mixture, and thionyl chloride (1.1 equivalent) was slowly added dropwise to the mixture, and the mixture was stirred at room temperature for 0.5 hour while monitoring the reaction with a time-plate every 0.5 hour (monitoring with petroleum ether: ethyl acetate 10: 1). After the reaction is finished, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system with the saturated sodium bicarbonate aqueous solution and saturated saline solution for three times, combining the organic solvents for three times, drying, filtering, and concentrating the organic phase to obtain a crude chloride product which is directly used for the next reaction. Step two: to the crude chloride obtained in the previous step, acetonitrile solvent (2mL) and triethylamine (1.2 eq) were added, the reaction was carried out at 80 ℃ for 3 hours, the reaction was monitored every 1.5 hours (petroleum ether: ethyl acetate 10:1 for chlorinated starting material, DCM: MeOH: 10:1 for quaternary ammonium salt product), after the reaction was completed, the reaction solution was concentrated by a rotary evaporator, after concentration, 50mL of dichloromethane was added to the concentrated solution, the mixture was washed and extracted three times with saturated brine, and the three organic phases were combined, dried, filtered, and concentrated. Then on a silica gel column, with dichloromethane: 20 parts of methanol: 1 eluting to obtain a purified target product.
Example 9(5- (aminomethyl) pyrrol-2-yl) dec-1-en-3-one
Figure BDA0003594970610000083
The synthesis steps are as follows: the method comprises the following steps: the compound obtained in example 7 (100mg, 1 equivalent) was dissolved in dichloromethane (4mL), cooled to 0 ℃, and then a solution of phosphorus tribromide (1.3 equivalents) in dichloromethane (4mL) was added dropwise thereto, and the mixture was further stirred for 1 hour, with the reaction being monitored every 0.5 hour on a time-plate. After the reaction is finished, washing with water, extracting with dichloromethane, drying with anhydrous sodium sulfate, and evaporating the solvent to obtain oily substance, namely crude bromide, which is directly used for the next reaction without further purification.
Step two: the bromide obtained in the first step was dissolved in a mixed solution of ether/ethanol (2 mL: 2mL), and aqueous ammonia (0.5mL) was added dropwise thereto, followed by stirring at room temperature for 5 hours. After the reaction is finished, washing with water, extracting with dichloromethane, drying with anhydrous sodium sulfate, evaporating the solvent to obtain oily matter which is a crude product of the target product, and then performing silica gel column chromatography on the oily matter by using petroleum ether: ethyl acetate 1:1 eluting to obtain a purified target product.
Example 10(5- (hydroxymethyl) thiophen-2-yl) dec-1-en-3-one
Figure BDA0003594970610000091
The synthesis steps are as follows: 5- (hydroxymethyl) -2-thiophenecarboxaldehyde (100mg, 1 eq), 2-nonanone (5 eq), 0.5M NaOH (0.57 eq, 0.9mL), MeOH (0.9mL), stirred at room temperature for 12 h, and the reaction monitored on a plaque at 5 hour intervals (monitored with petroleum ether PE: ethyl acetate EtOAc ═ 5: 1). After the reaction, 100mL of ethyl acetate is added, the mixture is washed and extracted for three times by saturated saline solution, an organic phase is collected, an aqueous phase is extracted for two times by ethyl acetate, the organic phases are combined, anhydrous magnesium sulfate or anhydrous sodium sulfate is added for drying, a drying agent is removed by filtration, the organic phase is concentrated, and the mixture is subjected to silica gel column chromatography by petroleum ether: ethyl acetate 10: 1-petroleum ether: ethyl acetate 5: gradient elution 1 to obtain the purified target product.
Example 11
(5- ((2- ((2-aminoethyl) amino) methyl) thiophen-2-yl) dec-1-en-3-one
Figure BDA0003594970610000092
The method comprises the following steps: to the compound (100mg, 1 eq) obtained in example 10 was added dichloromethane (1mL) to give a mixture, and thionyl chloride (1.1 eq) was slowly added dropwise to the mixture, which was stirred at room temperature for 0.5 hour, and the reaction was monitored on a plaque basis at 0.5 hour intervals (monitoring with petroleum ether: ethyl acetate 10: 1). After the reaction is finished, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system with the saturated sodium bicarbonate aqueous solution and saturated saline solution for three times, combining the organic solvents for three times, drying, filtering, and concentrating the organic phase to obtain a crude chloride product which is directly used for the next reaction.
Step two: adding acetonitrile solvent (2mL) and diethylenetriamine (1.1 equivalent) into the crude chloride obtained in the previous step, reacting for 3 hours at 80 ℃, monitoring the reaction every 1.5 hours, concentrating the reaction solution by using a rotary evaporator after the reaction is finished, adding 50mL dichloromethane into the concentrated solution after the concentration, washing and extracting for three times by using saturated saline solution, combining organic phases for three times, drying, filtering and concentrating. Then on a silica gel column, with dichloromethane: 20 parts of methanol: 1 eluting to obtain a purified target product.
Example 12
(5- (hydroxymethyl) phen-2-yl) dec-1-en-3-one
Figure BDA0003594970610000101
The synthesis steps are as follows: 3-hydroxybenzaldehyde (100mg, 1 eq), 2-nonanone (5 eq), 0.5M NaOH (0.57 eq, 0.9mL), MeOH (0.9mL), stirred at room temperature for 12 h, and the reaction was monitored on a plaque basis (with petroleum ether PE: ethyl acetate EtOAc: 5: 1) every 5 hours. After the reaction, 100mL of ethyl acetate is added, the mixture is washed and extracted for three times by saturated saline solution, an organic phase is collected, an aqueous phase is extracted for two times by ethyl acetate, the organic phases are combined, anhydrous magnesium sulfate or anhydrous sodium sulfate is added for drying, a drying agent is removed by filtration, the organic phase is concentrated, and the mixture is subjected to silica gel column chromatography by petroleum ether: ethyl acetate 10: 1-petroleum ether: ethyl acetate 5: gradient elution 1 to obtain the purified target product.
Example 13
N, N-diethyl-N- ((5- (3-oxo-1-en-1-yl) phen-2-yl) methyl) ethylamine chloride
Figure BDA0003594970610000102
The method comprises the following steps: to the compound (100mg, 1 eq) obtained in example 12 was added dichloromethane (1mL) to give a mixture, and thionyl chloride (1.1 eq) was slowly added dropwise to the mixture, which was stirred at room temperature for 0.5 hour, and the reaction was monitored on a plaque basis (with petroleum ether: ethyl acetate 10: 1) every 0.5 hour. After the reaction is finished, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system with the saturated sodium bicarbonate aqueous solution and saturated saline solution for three times, combining the organic solvents for three times, drying, filtering, and concentrating the organic phase to obtain a crude chloride product which is directly used for the next reaction.
Step two: to the crude chloride obtained in the previous step, acetonitrile solvent (2mL) and triethylamine (1.2 eq) were added, the reaction was carried out for 3 hours at 80 ℃, the reaction was monitored every 1.5 hours (the chlorinated starting material was monitored by petroleum ether: ethyl acetate 10:1, and the quaternary ammonium salt product was monitored by DCM: MeOH: 10: 1), after the reaction was completed, the reaction solution was concentrated by a rotary evaporator, after concentration, 50mL of dichloromethane was added to the concentrated solution, the mixture was extracted three times by washing with saturated brine, and the three organic phases were combined, dried, filtered, and concentrated. Then on a silica gel column, with dichloromethane: 20 parts of methanol: 1 eluting to obtain a purified target product.
Example 14
(6- (hydroxymethyl) pyridin-2-yl) dec-1-en-3-one
Figure BDA0003594970610000111
The synthesis steps are as follows: 6-hydroxymethylpyridinecarboxaldehyde (100mg, 1 eq), 2-nonanone (1 eq), 0.5M NaOH (0.57 eq, 0.9mL), MeOH (0.9mL), stirred at room temperature for 12 hours, and the reaction was monitored on a plaque basis (with petroleum ether PE: ethyl acetate EtOAc: 5: 1) every 5 hours. After the reaction, 100mL of ethyl acetate is added, the mixture is washed and extracted for three times by saturated saline solution, an organic phase is collected, an aqueous phase is extracted for two times by ethyl acetate, the organic phases are combined, anhydrous magnesium sulfate or anhydrous sodium sulfate is added for drying, a drying agent is removed by filtration, the organic phase is concentrated, and the mixture is subjected to silica gel column chromatography by petroleum ether: ethyl acetate 10: 1-petroleum ether: ethyl acetate 5: gradient elution 1 to obtain the purified target product.
Example 15(6- (aminomethyl) pyridin-2-yl) dec-1-en-3-one
Figure BDA0003594970610000112
The synthesis steps are as follows: the method comprises the following steps: the compound obtained in example 14 (100mg, 1 equivalent) was dissolved in dichloromethane (4mL), cooled to 0 ℃, and then a solution of phosphorus tribromide (1.3 equivalents) in dichloromethane (4mL) was added dropwise thereto, and the mixture was further stirred for 1 hour, with the reaction being monitored every 0.5 hour on a time-plate. After the reaction is finished, washing with water, extracting with dichloromethane, drying with anhydrous sodium sulfate, and evaporating the solvent to obtain oily substance, namely crude bromide, which is directly used for the next reaction without further purification.
Step two: the bromide obtained in the first step was dissolved in a mixed solution of ether/ethanol (2 mL: 2mL), and aqueous ammonia (0.5mL) was added dropwise thereto, followed by stirring at room temperature for 5 hours. After the reaction is finished, washing with water, extracting with dichloromethane, drying with anhydrous sodium sulfate, evaporating the solvent to obtain oily matter which is a crude product of the target product, and then performing silica gel column chromatography on the oily matter by using petroleum ether: ethyl acetate 1:1 eluting to obtain a purified target product.
Example 16 evaluation of weight loss on static
400mL of 1mol/L HCl solution is added into a 500mL glass bottle, the temperature is raised to 60 ℃, and a pretreated Q235 steel sheet is placed into the glass bottle to be corroded for 4 hours. After the corrosion reaction is finished, taking out the test piece, and carrying out test post-treatment on the test piece by referring to SY5273-2014 Corrosion inhibitor performance index and evaluation method for oilfield produced water treatment: soaking in acid pickling solution for 2min, cleaning with decontamination powder, soaking in ethanol solution for dewatering, blow-drying with cold air, weighing, calculating corrosion rate, and comparing with blank and known water-soluble imidazoline quaternary ammonium salt corrosion inhibitor.
Wherein the known water-soluble imidazoline quaternary ammonium salt corrosion inhibitor has a structural formula as follows:
Figure BDA0003594970610000121
the corrosion rate was calculated as follows:
Figure BDA0003594970610000122
wherein V is the corrosion rate, mm/a
Δ W is the weight difference of the sample before and after corrosion, g;
s is the area of the test piece, cm2；
Rho is the density of the test piece, 7.85g/cm3；
t is the time for carrying out the experiment, h;
the specification of the carbon steel is 40X 13X 2(mm)
The results of the static weight loss evaluation are shown in table 1.
TABLE 1 results of static weightlessness evaluation
Figure BDA0003594970610000123
Figure BDA0003594970610000131
As can be seen from the above table data, the α, β -unsaturated ketone compound of the present invention exhibits a very strong corrosion resistance effect on carbon steel as an organic corrosion inhibitor. After carbon steel treatment, the corrosion rates of the samples 1-B and 1-G are excellent, and are reduced by about 5 times compared with the corrosion rate of the known water-soluble imidazoline quaternary ammonium salt corrosion inhibitor.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. An alpha, beta-unsaturated ketone compound is characterized in that the alpha, beta-unsaturated ketone compound is selected from at least one of a compound with a structural formula shown in a formula I and a compound with a structural formula shown in a formula II;
Figure FDA0003594970600000011
in formula I, formula II, Y1Any one selected from methylene and N, O, S; y is2Any one selected from methine and N;
R1is selected from C1-C24Any one of alkyl groups of (a);
R2selected from amino, hydroxy, oxo-OSO3M, polyethoxy ether group, substituted amino group, polyethylamino group, perylene-NR3 +X1 -Any one of (a) to (b);
m is selected from any one of Na, K and Li;
R3is selected from C1-C6Alkyl, substituted C1-C6Alkyl of (C)6-C12Any one of the aryl groups of (a);
X1selected from halogens.
2. The α, β -unsaturated ketone compound according to claim 1, wherein the substituent in the substituted amino group is selected from C6-C12Any of the aryl groups of (1).
3. The α, β -unsaturated ketone compound according to claim 1, wherein the number of ethoxy units in the polyethoxy ether group is 1 to 10;
the number of ethylamine units in the polyethylamine group is 1-10;
said substituted C1-C6The substituents in the alkyl group of (A) are selected from C6-C12Any of the aryl groups of (1).
4. A process for the preparation of α, β -unsaturated ketones according to any of claims 1 to 3, characterized in that it comprises:
reacting a mixture containing a compound I and a compound ii in the presence of an alkaline substance to obtain the alpha, beta-unsaturated ketone compound P;
r in the alpha, beta-unsaturated ketone compound P2Is a hydroxyl group;
the compound i is selected from any one of a compound with a structural formula shown in a formula III and a compound with a structural formula shown in a formula IV;
Figure FDA0003594970600000021
the compound ii is selected from any one of compounds with a structural formula shown in a formula V;
Figure FDA0003594970600000022
alternatively, the first and second electrodes may be,
(a) mixing the alpha, beta-unsaturated ketone compound P with a halogenating reagent, and reacting II to obtain a halogenated intermediate product K;
(b) reacting said halogenated intermediate K with a compound containing R2Reacting III with nucleophilic reagent to obtain the alpha, beta-unsaturated ketone compound O;
r in the alpha, beta-unsaturated ketone compound O2Selected from amino, -OSO3M, polyethoxy ether group, substituted amino group, polyethamino group, -NR3 +X1 -Any one of (a);
alternatively, the first and second electrodes may be,
mixing the alpha, beta-unsaturated ketone compound P with pyridine sulfate to react IV to obtain the alpha, beta-unsaturated ketone compound Q;
r in the alpha, beta-unsaturated ketone compound Q2is-OSO3M。
5. The method according to claim 4, wherein the conditions of reaction I are as follows: the reaction temperature is 20-30 ℃; the reaction time is 18-24 h;
the conditions of the reaction II are as follows: the reaction temperature is 10-20 ℃; the reaction time is 0.5 to 4 hours;
the conditions of the reaction III are as follows: the reaction temperature is 50-100 ℃; the reaction time is 0.5 to 5 hours;
the conditions of the reaction IV are as follows: the reaction temperature is 20-30 ℃; the reaction time is 0.5 h-2 h.
6. The process according to claim 4, wherein in the step (a), the halogenating agent is at least one selected from thionyl chloride, oxalyl chloride, phosphorus oxychloride, concentrated hydrochloric acid, phosphorus tribromide;
said compound containing R2The nucleophilic reagent is at least one selected from triethylamine, tributylamine, tribenzylamine, aniline, diethylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, pentaethylene glycol, octaethylene glycol, N' -bis (2-aminoethyl) -1, 3-propanediamine, diethylenetriamine, triethylenetetramine and 1, 8-diamino-3, 6-dioxaoctane.
7. The method according to claim 4, wherein the molar ratio of the compound i to the compound ii is 0.5-1: 1-10;
in the step (a), the alpha, beta-unsaturated ketone compound P, a halogenating agent and a compound containing R2The mol ratio of the nucleophilic reagent is 0.5-1:1-10: 1-10;
the mol ratio of the alpha, beta-unsaturated ketone compound P to the pyridine sulfate is 0.5-1: 1-10.
8. The method according to claim 4, wherein the alkali is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, and potassium phosphate.
9. Use of at least one of the α, β -unsaturated ketone compounds according to any one of claims 1 to 3, and the α, β -unsaturated ketone compounds prepared by the method according to any one of claims 4 to 8, as corrosion inhibitors.
10. Use according to claim 9, wherein the corrosion inhibitor is used for corrosion protection of carbon steel.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535315A (en) * 2006-10-13 2009-09-16 辉瑞有限公司 Heterocyclic compounds useful as anabolic agents for livestock animals
US20150232394A1 (en) * 2011-09-14 2015-08-20 Los Alamos National Security, Llc Compounds and methods for the production of long chain hydrocarbons from biological sources
CN109718850A (en) * 2017-10-31 2019-05-07 中国科学院大连化学物理研究所 A method of preparing aviation kerosine presoma

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852278A (en) * 1973-01-22 1974-12-03 Rohm & Haas Preparation of 4-(2-(furfurylideneamino)-phenyl)-3-thioallophanates
US20170226075A1 (en) * 2014-08-19 2017-08-10 Archer Daniels Midland Company Synthesis of Non-Ionic Surfactants From 5-Hydroxymethyl-2-Furfural, Furan-2,5-Dimethanol and Bis-2,5-Dihydroxymethyl-Tetrahydrofurans
EP3221301A4 (en) * 2014-11-21 2018-04-18 Archer Daniels Midland Company Acid-catalyzed acylation of 5-(hydroxylmethyl)-furfural reduction products

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535315A (en) * 2006-10-13 2009-09-16 辉瑞有限公司 Heterocyclic compounds useful as anabolic agents for livestock animals
US20150232394A1 (en) * 2011-09-14 2015-08-20 Los Alamos National Security, Llc Compounds and methods for the production of long chain hydrocarbons from biological sources
CN109718850A (en) * 2017-10-31 2019-05-07 中国科学院大连化学物理研究所 A method of preparing aviation kerosine presoma

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CACCHI, S. ET AL.: "A one-pot palladium-catalyzed synthesis of β,β-diaryl ketones and aldehydes from aryl iodides and α,β-unsaturated carbonyl compounds", 《SYNTHESIS》, no. 7, pages 575 *
CAS数据库: "RN：2307878-65-3", 《REGISTRY》, pages 1 *
GALKIN, KONSTANTIN I. ET AL.: "Towards Improved Biorefinery Technologies: 5-Methylfurfural as a Versatile C6 Platform for Biofuels Development", 《CHEMSUSCHEM》, vol. 12, no. 1, pages 185 - 189 *
W. W. FRENIEF ET AL.: "新型盐酸缓蚀剂α-链烯基苯酮", 《化学清洗》, pages 14 - 16 *
狄志刚等: "水性水喷砂防锈剂的研制及应用研究", 《涂料工业》, vol. 51, no. 12, pages 37 - 43 *
颜涛等: "一种β氨基酮缓蚀剂的合成及缓蚀性能", 《化工技术与开发》, vol. 47, no. 10, pages 5 - 8 *
颜肖慈等: "呋喃及其衍生物对铝缓蚀机理的量子化学研究", 《中国腐蚀与防护学报》, vol. 19, no. 6, pages 372 - 375 *

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